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  • 新型納米裂紋結構隔膜的設計及其在鋰離子電池中的應用

    Design of novel nanocrack-structured separators and their application in lithium-ion batteries

    • 摘要: 隔膜是電池的關鍵組件,能夠提供離子傳輸通道并防止正負極接觸短路,對儲能系統的穩定運行至關重要. 目前商業化鋰離子電池隔膜主要通過干法和濕法工藝生產,盡管各類二次電池技術發展迅猛,但高端隔膜技術仍依賴進口,成為制約儲能產業發展的瓶頸,開發高性能隔膜已成為當前研究的重中之重. 傳統濕法隔膜制備工藝的隔膜孔徑分布和孔隙率可控,但其需大量使用洗脫溶劑,導致能耗高、工藝復雜且成本較高. 本工作提出一種利用聚對苯二甲酸–己二酸丁二醇酯(PBAT)和等規聚丙烯(IPP)的相容性差異,采用簡單的熔融共混–吹塑工藝實現聚合物微相分離,構建形成具有均勻的納米裂紋結構的新型電池隔膜以實現離子傳輸(離子傳導率達0.25 mS·cm?1). 該隔膜制備工藝省去傳統濕法和干法隔膜工藝中的造孔步驟(溶劑洗脫或拉伸定型工序),顯著提升生產效率并降低能耗. 所制備隔膜表現出優異力學性能,橫、縱向極限拉伸強度分別為7.52 MPa和21.74 MPa,應變高達392.41%和597.58%. 組裝Li//LiFePO4電池后,在0.1 C電流密度下首周放電比容量達155.99 mA·h·g?1,循環100次后容量保持率為92.9%,驗證了該工藝的可行性. 該研究為新型電池隔膜設計與工藝研發提供了新的思路.

       

      Abstract: The separator, which provides an ion transport pathway while preventing short circuits between electrodes, is an essential component of secondary metal batteries and plays a pivotal role in the stable operation of energy storage systems. Currently, commercial lithium-ion battery separators are primarily prepared using dry and wet methods. Despite rapid advancements in various secondary energy storage systems, the domestic high-end separator market remains heavily reliant on imports, posing a bottleneck to the development of the energy storage industry. This dependence is due to not only the quality of raw materials but also the lack of precision separator production equipment. Consequently, developing high-performance separators based on new materials and preparation technologies has become a top priority in current research. Although traditional wet-process separator fabrication offers controllable pore size distribution and porosity, it requires extensive use of extraction solvents, leading to high energy consumption, complex procedures, and elevated costs. The dry process demands high-quality raw materials and involves complex production steps, increasing costs and production difficulty. According to the principle of similar compatibility, polymers with different polarities generally exhibit poor compatibility. Phase separation can form an interphase between polymers with significant polarity differences. Inevitably, weak interactions near this interphase result in a loose structure that allows ion transport. Abundant interphases can form sufficient ion channels for migration between the cathode and anode. Herein, owing to the insufficient compatibility of poly(butylene adipate-co-terephthalate) (PBAT) and isostatic polypropylene (IPP), we developed a novel nanocrack-structured separator with uniform microphase separation by blending via the blow molding process, enabling efficient ion transport with an ionic conductivity of 0.25 mS·cm?1. In traditional wet processes, pore-making involves the elution of pore-forming agents with bulk organic solvents and drying steps. The heat drawing and cooling parameters play key roles in forming long, narrow pore morphologies in the dry process. In comparison, the new preparation technology for nanocrack-structured separators is simple and mature, omitting the pore-making step. Furthermore, this low-equipment-cost process is suitable for large-scale production. The abundant nanocracks at the polymer interfaces maintain sufficient ion transport flux for normal charge-discharge processes. This method significantly enhances production efficiency while reducing energy consumption. Moreover, the prepared separator demonstrates superior mechanical properties, with transverse and longitudinal ultimate tensile strengths of 7.52 MPa and 21.74 MPa, respectively, and strains reaching 392.41% and 597.58%. The excellent ion conductivity and mechanical properties of the nanocrack-structured separator satisfy battery separator requirements. When assembled into Li//LiFePO4 batteries, the battery delivers an initial discharge capacity of 155.99 mA·h·g?1 at a current density of 0.1 C, with 92.9% capacity retention after 100 cycles, validating the application feasibility of this nanocrack-structured separator and preparation process. This study successfully eliminates the pore-forming step typical in traditional separator preparation, achieving dual benefits of reduced energy consumption and environmental protection. Furthermore, it innovatively utilizes nanocrack structures for ion transport, expanding applications in electrochemical energy storage and providing novel insights for advancing battery separator fabrication technologies.

       

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